Semiconductor processing methods of transferring patterns from patterned photoresists to materials, and structures comprising silicon nitride

ABSTRACT

The invention includes a semiconductor processing method. A first material comprising silicon and nitrogen is formed. A second material is formed over the first material, and the second material comprises silicon and less nitrogen, by atom percent, than the first material. An imagable material is formed on the second material, and patterned. A pattern is then transferred from the patterned imagable material to the first and second materials. The invention also includes a structure comprising a first layer of silicon nitride over a substrate, and a second layer on the first layer. The second layer comprises silicon and is free of nitrogen. The structure further comprises a third layer consisting essentially of imagable material on the second layer.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.09/488,947 which was filed on Jan. 18, 2000 now U.S. Patent No.6,440,860 and which is incorporated by reference herein.

TECHNICAL FIELD

The invention pertains to methods of transferring patterns fromphotoresists to materials, and also pertains to structures comprisingsilicon nitride.

BACKGROUND OF THE INVENTION

A commonly utilized process for patterning structures utilized forintegrated circuitry is photolithographic processing. An imagablematerial (typically photoresist) is provided over a mass which isultimately to be patterned. Portions of the imagable material are thenexposed to radiation, while other portions remain unexposed (in the caseof photoresist, the radiation is light). After the exposure, thematerial is subjected to conditions which selectively remove either theportions of the exposed to radiation, or the portions which were notexposed to radiation. If the imagable material comprises photoresist andthe portions exposed to radiation are removed, the photoresist isreferred to as a positive photoresist, whereas if the portions which arenot exposed to radiation are removed the photoresist is referred to as anegative photoresist. Once the imagable material is patterned, it isutilized as a masking layer for patterning the underlying mass.Specifically, the patterned imagable material covers some portions ofthe mass, while leaving other portions exposed to an etch which removesthe exposed portions. Accordingly, the mass remaining after the etch isin approximately the same pattern as the patterned imagable materialformed over the mass.

Photolithographic processing is utilized for patterning numerousmaterials, including silicon nitride. However, problems can occur duringthe utilization of photolithographic processing for patterning siliconnitride. Specifically, the pattern formed in silicon nitride isfrequently not the same as the pattern which was intended to be formedin the photoresist. Such problem can be particularly severe whenutilizing photoresist patterned with deep UV light processing, whereindeep UV light is defined as ultraviolet light having a wavelength ofless than or equal to 248 nanometers. It would be desirable to developmethods for avoiding the above-discussed problems.

SUMMARY OF THE INVENTION

In one aspect, the invention includes a semiconductor processing method.A first material comprising silicon and nitrogen is formed. A secondmaterial is formed over the first material, and the second materialcomprises silicon and less nitrogen (by atom percent) than the firstmaterial. An imagable material is formed on the second material, andpatterned. A pattern is then transferred from the patterned imagablematerial to the first and second materials.

In another aspect, the invention encompasses a method of forming apatterned structure. A first layer comprising silicon and nitrogen isformed over a substrate. A sacrificial layer is formed on the firstlayer, and comprises less nitrogen (by atom percent) than the firstlayer. A layer of imagable material is formed on the sacrificial layerand patterned. The patterned structure has a pair of opposing sidewallsextending upwardly from the substrate. A pair of opposing corners aredefined where the sidewalls join the substrate. The opposing corners arecloser to one another than they would be if the sacrificial layer wasabsent and the imagable material was on the first layer during thepatterning of the imagable material. The sacrificial layer is removedfrom the patterned structure.

In yet another aspect, the invention encompasses a structure comprisinga first layer of silicon nitride over a substrate, and a second layer onthe first layer. The second layer comprises silicon and is free ofnitrogen. The structure further comprises a third layer consistingessentially of imagable material on the second layer.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred embodiments of the invention are described below withreference to the following accompanying drawings.

FIG. 1 is a fragmentary, diagrammatic, cross-sectional view of asemiconductor wafer fragment.

FIG. 2 is a view of the FIG. 1 fragment shown at a processing stepsubsequent to that of FIG. 1.

FIG. 3 is a view of the FIG. 1 fragment shown at a processing stepsubsequent to that of FIG. 2.

FIG. 4 is a diagrammatic, fragmentary, cross-sectional view of asemiconductor wafer fragment.

FIG. 5 is a view of the FIG. 4 fragment shown at a processing stepsubsequent to that of FIG. 4.

FIG. 6 is a view of the FIG. 4 fragment shown at a processing stepsubsequent to that of FIG. 5.

FIG. 7 is a view of the FIG. 4 fragment shown at a processing stepsubsequent to that of FIG. 6.

FIG. 8 is a view of the FIG. 4 fragment shown at a processing stepsubsequent to that of FIG. 7.

FIG. 9 is a view of the FIG. 4 fragment shown at a processing stepsubsequent to that of FIG. 8 in accordance with an embodiment of thepresent invention.

FIG. 10 is a view of the FIG. 4 fragment shown at a processing stepsubsequent to that of FIG. 8 in accordance with another embodiment ofthe present invention.

FIG. 11 is a photograph of a semiconductor wafer fragment havingstructures formed thereover by a particular patterning method.

FIG. 12 is a view of a semiconductor wafer fragment having structuresformed thereover by a processing method different than that utilized forforming the structures of FIG. 11.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This disclosure of the invention is submitted in furtherance of theconstitutional purposes of the U.S. Patent Laws “to promote the progressof science and useful arts” (Article 1, Section 8).

A method of utilizing photoresist for patterning a silicon nitridematerial is described with reference to FIGS. 1-3. Referring to FIG. 1,a semiconductor wafer fragment 10 is illustrated at a preliminary stepof the method. Fragment 10 comprises a substrate 12 having an uppersurface 15. Substrate 12 can comprise, for example, monocrystallinesilicon. To aid in interpretation of the claims that follow, the terms“semiconductive substrate” and “semiconductor substrate” are defined tomean any construction comprising semiconductive material, including, butnot limited to, bulk semiconductive materials such as a semiconductivewafer (either alone or in assemblies comprising other materialsthereon), and semiconductive material layers (either alone or inassemblies comprising other materials). The term “substrate” refers toany supporting structure, including, but not limited to, thesemiconductive substrates described above.

Layers 16, 18, 20, 22 and 24 are formed over upper surface 15, and areultimately to be patterned into a wordline. Accordingly, layer 16comprises silicon dioxide, layer 18 comprises conductively doped silicon(i.e., silicon doped to a concentration of at least about 10¹⁸ atoms/cm³with a conductivity enhancing dopant), layer 20 comprises a metal (suchas, for example, tungsten or titanium), and layer 22 comprises siliconnitride. Layer 22 has an upper surface 23, and layer 24 is formed on(i.e., against) such upper surface. Layer 24 comprises an imagablematerial, and is described herein to comprise photoresist. It is to beunderstood, however, that the term “imagable material” can encompassesmaterials patterned by radiation (or energy) other than light, and canaccordingly encompass materials other than photoresist.

Referring to FIG. 2, photoresist 24 is patterned to form blocks 26. Suchpatterning can comprise, for example, exposing portions of thephotoresist to radiation while leaving other portions unexposed, andsubsequently selectively removing either the exposed or unexposedportions with a solvent.

Blocks 26 comprise sidewalls 28 which are preferably substantiallyperpendicular to upper surface 23 of silicon nitride layer 22. However,a problem which occurs during the patterning of photoresist 24 is thatphotoresist adjacent blocks 26 does not remove as well as photoresistwhich is further removed from blocks 26. Such results in the formationof foot portions 30 at locations where sidewalls 28 join upper surface23 of silicon nitride layer 22.

Referring to FIG. 3, blocks 26 are utilized as a mask during an etch ofunderlying layers 16, 18, 20 and 22 to form wordline stacks 40 fromlayers 16, 18, 20 and 22. Wordline stacks 40 comprise sidewalls 41 whichare substantially perpendicular to upper surface 15 of substrate 12.

As shown, foot portions 30 (FIG. 2) are variabily eroded duringformation of wordline stacks 40 so that the stacks have laterallyextending portions 42 where the stacks join with substrate 12. Footportions 30 cause laterally extending portions 42 because thephotoresist of foot portions 30 is etched by the conditions which etchlayers 16, 18, 20 and 22, and is ultimately removed to allow portions oflayers 16, 18, 20 and 22 beneath foot regions 30 to be removed. However,the portions of layers 16, 18, 20 and 22 beneath foot regions 30 areexposed to etching conditions for less time than are portions of layers16, 18, 20 and 22 that are not beneath foot portions 30. Accordingly,the portions beneath foot portions 30 are etched less than are portionsof layers 16, 18, 20 and 22 not beneath foot portions 30, causingformation of laterally extending portions 42. The laterally extendingportions 42 extend into a gap between adjacent wordline stacks 40, andthus can affect a critical dimension of a structure (such as aconductive plug or capacitor) subsequently formed between stacks 40.

Sidewalls 41 join upper surface 15 of substrate 12 at a pair of opposingcorners 43 relative to one of stacks 40, and a pair of opposing corners45 relative to another of stacks 40. In many applications it would bedesirable if the opposing corners relative to a particular stack were asclose together as possible after the patterning of layers 16, 18, 20 and22. However, laterally extending portions 42 extend a distance betweenthe opposing corners 43, and likewise extend a distance between opposingcorners 45.

An aspect of the present invention is a recognition that foot portions30 of FIG. 2 are due primarily to the formation of imagable materialdirectly on silicon nitride layer 22, and accordingly can be alleviated(or even eliminated) by forming another material between silicon nitridelayer 22 and imagable material 24. An embodiment of the presentinvention is described with reference to a wafer fragment 10 a of FIG.4. In referring to FIG. 4, similar numbering will be used as was usedabove in describing FIGS. 1-3, with differences indicated by the suffix“a”, or by different numerals.

Wafer fragment 10 a of FIG. 4, like wafer fragment 10 of FIG. 1,comprises a substrate 12, a silicon dioxide layer 16, aconductively-doped silicon layer 18, a metal layer 20, and a siliconnitride layer 22. However, fragment 10 a of FIG. 4 differs from fragment10 of FIG. 1 in that a imagable-material-supporting mass (or layer) 50is provided over silicon nitride layer 22. Layer 50 comprises adifferent material than silicon nitride layer 22. In particularembodiments, layer 50 comprises less nitrogen (by atom percent) thansilicon nitride layer 22. For instance, layer 50 can consist essentiallyof either silicon or conductively doped silicon, and can accordingly besubstantially free of nitrogen (with the term “substantially free”understood to mean that layer 50 comprises less than about 10% of theatom percentage of nitrogen of layer 22, and can comprise no nitrogen).Alternatively, layer 50 can consist entirely of silicon or conductivelydoped silicon, and accordingly be entirely free of nitrogen.

If layer 50 is to comprise, consist of, or consist essentially of eithersilicon or conductively doped silicon, such layer can be formed bychemical vapor deposition of silicon or polysilicon over layer 22. Forinstance, the silicon can be deposited utilizing silane, dichlorosilane,or gases of the general formula Si_(x)H_((2x+2)). Preferably, if layer50 comprises a conductive material, such layer is formed to be less than150 Angstroms thick, and more preferably less than 100 Angstroms thick,to enable the layer to be easily removed in subsequent processing.Procedures which can be utilized to form such thin silicon layers areatomic layer deposition (ALD), or low pressure chemical vapor deposition(LPCVD) utilizing a pressure of less than 100 mTorr, at a temperature ofless than 550° C. Alternative procedures which could be used for formingthin silicon layers include chemical vapor deposition utilizing apressure of less than or equal to about 1 Torr, and a temperature ofless than or equal to about 650° C.

In an alternative embodiment of the invention, layer 50 can compriseoxygen, and can, for example, comprise, consist of, or consistessentially of silicon dioxide. If layer 50 is to consist of, or consistessentially of silicon dioxide, such layer can be formed by depositingsilicon dioxide over layer 22. Alternatively, if layer 50 is to comprisesilicon dioxide, such layer can be formed by subjecting an upper surfaceof layer 22 to oxidizing conditions. The oxidation of silicon nitridelayer 22 can comprise, for example, exposing such layer to anoxygen-containing gas, such as, for example, O₂, O₃, N₂O, NO, etc.

If layer 50 is formed by oxidizing an upper portion of silicon nitridelayer 22, the resulting structure can be considered to comprise asilicon nitride material which includes both layer 50 and layer 22, withlayer 50 being considered an oxidized portion of the silicon nitridematerial and layer 22 being considered a non-oxidized portion of thematerial. Further, the oxidized portion defined by layer 50 can beconsidered to be an oxide cap over the non-oxidized portion.

One method of improving the oxidation of an outer portion of a siliconnitride layer relative to an inner portion is to form the outer portionto have a higher relative concentration of silicon to nitrogen than doesthe inner portion. A silicon nitride material having a differentrelative concentration of silicon to nitrogen at one portion than atanother portion can be formed by a chemical vapor deposition (CVD)process utilizing a silicon precursor gas (for example, SiH₂Cl₂(dichlorosilane)) and a nitrogen precursor gas (for example, NH₃(ammonia)). In an exemplary process, a substrate is provided within aCVD reaction chamber together with a first ratio of a silicon precursorgas to a nitrogen precursor gas. One portion of silicon nitride layer 22is then deposited. Subsequently, the ratio of the silicon precursor gasto the nitrogen precursor gas is increased and the other portion of thesilicon nitride layer is deposited. Exemplary processing conditions forthe CVD process include a pressure of from about 100 mTorr to about 1Torr, and a temperature of from about 700° C. to about 800° C.

In yet another embodiment, layer 50 can comprise silicon, oxygen, andnitrogen, but comprises less nitrogen (by atom percent) than does layer22. Layer 50 can be formed by, for example, depositing Si_(x)O_(y)N_(z)utilizing dichlorosilane and N₂O, wherein x is greater than 0 and lessthan 1, y is greater than 0 and less than 1, and z is greater than 0 andless than 1. Alternatively, layer 50 can be formed from bis-(tertiarybutyl amino)-silane (BTBAS).

Referring to FIG. 5, an imagable material layer 24 is formed overimagable-material-supporting layer 50. Imagable material layer 24 isreferred to below as comprising photoresist, but it is to be understoodthat layer 24 can comprise other imagable materials besides photoresist.

Referring to FIG. 6, photoresist 24 is patterned by exposing someportions of resist 24 to radiation while leaving other portionsunexposed, and then utilizing a solvent to selectively remove either theexposed or unexposed portions of the photoresist. The patterning formsphotoresist 24 into blocks 26 a. Blocks 26 a comprise sidewalls 28 a.Blocks 26 a differ from blocks 26 of FIG. 4 . in that foot portions 30(FIG. 4) are missing from blocks 26 a. Accordingly, sidewalls 28 a ofblocks 26 a extend substantially perpendicularly from an upper surfaceof material 50.

Referring to FIG. 7, a pattern is transferred from blocks 26 a tounderlying materials 16, 18, 20, 22 and 50 to form patterned structures60 comprising the materials of layers 16, 18, 20, 22 and 50. Patternedstructures 60 comprise sidewalls 61 which are coextensive with sidewalls28 a of blocks 26 a, and which extend perpendicularly relative to anupper surface of substrate 12. A difference between sidewalls 61 of FIG.7 and sidewalls 41 of FIG. 3 is that sidewalls 61 lack laterallyextending portions (such as the laterally extending portions 42 shown inFIG. 3). Sidewalls 61 join substrate 12 to form opposing corners 63relative to one of the stacks 60, and opposing corners 65 relative toanother of the stacks 60. Opposing corners 63 are closer to one anotherthan opposing corners 43 (FIG. 3), due to the lack of lateral extendingportions 42 (FIG. 3) in the FIG. 7 structure. Likewise, opposing corners65 are closer to one another than opposing corners 45 (FIG. 3). Thestructure shown in FIG. 7 can be considered to comprise a first layer 22of silicon nitride over a substrate 20. Such structure can furthercomprise a second layer 50 which comprises silicon and is free ofnitrogen on first layer 22. Additionally, the structure can comprise athird layer 24 consisting essentially of imagable material on secondlayer 50. Third layer 24 can be, for example, photoresist, and secondlayer 50 can consist essentially of silicon, conductively doped silicon,or silicon dioxide.

Referring to FIG. 8, photoresist blocks 26 a (FIG. 7) are removed and amaterial 66 is formed over patterned stacks 60, as well as oversubstrate 12. Material 66 can comprise, for example, an inorganic andelectrically insulative material, such as, for example, silicon dioxideor silicon nitride. Material 66 can be formed by, for example, chemicalvapor deposition.

The structure of FIG. 8 can be considered to comprise a layer of siliconnitride 22 over a substrate (with the substrate understood to comprisematerial 12 and layers 16, 18, and 20). The structure further compriseslayer 50 over silicon nitride layer 22, and a layer 66 formed on (i.e.,against) layer 50. Layer 66 can consist essentially of inorganicmaterial, such as, for example, silicon nitride, silicon dioxide, orSi_(x)O_(y)N_(z) (wherein x, y and z are greater than 0), and cancomprise a different chemical composition than layer 50. In thestructure of FIG. 8, layers 22 and 50 are part of a stack 60 comprisinga pair of substantially planar opposing sidewalls 61. Further in thestructure of FIG. 8, layer 66 is over the stack 60 comprising layers 50and 22, as well as along sidewalls 61 of the stack.

FIGS. 9 and 10 illustrate alternative processing which can occurrelative to the FIG. 8 structure. Referring first to FIG. 9, material 66is subjected to anisotropic etching conditions which forms material 66into spacers 70 extending along sidewalls 61 of stack 60. Suchanisotropic etching is conducted for a sufficient period of time toentirely remove material 50 (FIG. 8) from over silicon nitride material22. The processing of FIG. 9 can be preferred in embodiments in whichmaterial 50 comprises a conductive material, such as, for example,conductively doped silicon. If material 50 were not removed in suchembodiments, it could short conductive components across an uppersurface of stacks 60. The processing of FIG. 9 can be easier to utilizeif material 50 is kept thin (i.e., less than 150 Angstroms thick, andmore preferably less than 100 Angstroms thick), as the material can thenbe removed with less etching than could a thicker material. It is notedthat substrate 12 may be etched during the removal of material 50. Suchetching into substrate 12 is shown in FIG. 8 as trenches 72 formedwithin regions of substrate 12 that are not covered by spacers 70 orstacks 60.

Material 50 can be considered a sacrificial material relative to themethod of FIGS. 4-9. Specifically, the material is provided in theprocessing of FIGS. 4-6 to improve patterning of a photoresist material,and subsequently removed in the processing of FIG. 9.

The processing of FIG. 10 is similar to that of FIG. 9 in that material66 of FIG. 8 is etched to form spacers 70. However, the processing ofFIG. 10 differs from that of FIG. 9 in that material 50 remains afterthe etch of material 66. The processing of FIG. 10 can be preferred inembodiments in which material 50 consists of an electrically insulativematerial, such as, for example, silicon dioxide, or undoped silicon. Ifthe processing of FIG. 10 is utilized, and if material 50 comprises aninsulative material, there can be less preference to keeping thematerial to a thickness of less than 150 Angstroms relative to theadvantages of keeping material 50 to a thickness below 150 Angstroms ifthe material is electrically conductive and to be removed by theprocessing of FIG. 9.

An improvement which can be obtained utilizing photoresist-supportingmask 50 between a layer of photoresist and a layer of silicon nitrideduring patterning of the photoresist is evidenced by the photographs ofFIGS. 11 and 12. Specifically, FIG. 11 shows a structure whereinphotoresist is patterned while on silicon nitride, and FIG. 12 shows astructure wherein photoresist is patterned while on a layer of amorphoussilicon that is conductively doped to concentration of about 10²⁰atoms/cm³ with phosphorus. The structure of FIG. 11 shows photoresistblocks which join an underlying substrate at corners which are less than90° (and which specifically comprise foot portions at the locationswhere the sidewalls join the underlying substrate), whereas thestructure of FIG. 12 shows photoresist blocks which join an underlyingsubstrate at corners which are about 90°.

EXAMPLES Example 1

A silicon nitride layer is formed by chemical vapor deposition withdichlorosilane and ammonia at a temperature of from about 600° C. toabout 800° C. Subsequently, a layer of silicon is formed on the siliconnitride by chemical vapor deposition utilizing silane at a temperatureof from about 500° C. to about 700° C. The silicon can then be utilizedto support a layer of photoresist formed over the silicon nitride.

Example 2

A silicon nitride layer is formed by chemical vapor deposition withdichlorosilane and ammonia at a temperature of from about 600° C. toabout 800° C. Subsequently, a layer of silicon is formed on the siliconnitride by chemical vapor deposition utilizing silane at a temperatureof from about 500° C. to about 700° C. Finally, the silicon is oxidizedby exposure to one or more of N₂O, NO, O₂, O₃, at a temperature of from500° C. to about 800° C. Such forms a layer of silicon dioxide on thesilicon nitride. The silicon dioxide can then be utilized to support alayer of photoresist formed over the silicon nitride.

In compliance with the statute, the invention has been described inlanguage more or less specific as to structural and methodical features.It is to be understood, however, that the invention is not limited tothe specific features shown and described, since the means hereindisclosed comprise preferred forms of putting the invention into effect.The invention is, therefore, claimed in any of its forms ormodifications within the proper scope of the appended claimsappropriately interpreted in accordance with the doctrine ofequivalents.

1. A semiconductor processing method, comprising: providing a substratehaving an exposed metal layer; forming a layer of silicon nitride on themetal layer; depositing a nitrogen-free material consisting essentiallyof silicon on and in direct physical contact with the silicon nitride;forming an imagable material on the nitrogen-free material; patterningthe imagable material; transferring a pattern from the patternedimagable material to the nitrogen-free material, the metal layer, andthe silicon nitride the patterned silicon nitride comprising a sidewall;after transferring the pattern, removing the imagable material; forminga layer of silicon-comprising material over the nitrogen-free material;and etching the layer of silicon-comprising material to form a spaceralong the sidewall, the etching also removing the nitrogen-free materialfrom over the silicon nitride.
 2. The method of claim 1 wherein theimagable material is photoresist.
 3. The method of claim 1 wherein theimagable material is photoresist and the patterning comprises exposingthe photoresist to deep UV radiation.
 4. The method of claim 1 whereinthe nitrogen-free material consists essentially of conductively-dopedsilicon.
 5. The method of claim 1 wherein the silicon-comprisingmaterial comprises silicon nitride.
 6. The method of claim 1 wherein thenitrogen-free material comprises conductively-doped silicon and thesilicon-comprising material comprises silicon nitride.
 7. Asemiconductor processing method, comprising: providing a metal layerover a substrate; forming a first material comprising silicon andnitrogen on the metal layer; forming a second material on and in directphysical contact with the first material, the second material comprisingsilicon and less than 10% nitrogen, by atom percent; forming an imagablematerial on and in direct physical contact with the second material;patterning the imagable material; transferring a pattern from thepatterned imagable material to the first and second materials, thepatterned first material comprising a sidewall; removing the imagablematerial from on the second material; after removing the imagablematerial, forming a third material on and in direct physical contactwith the second material, wherein the third material consistsessentially of one of silicon dioxide or Si_(x)O_(y)N_(z), wherein x, yand z are each greater than 0; and etching the layer of third materialto form a spacer along the sidewall, the etching also removing thesecond material from over the first material.
 8. The method of claim 7wherein the imagable material is photoresist.
 9. The method of claim 7wherein the imagable material is photoresist and the patterningcomprises exposing the photoresist to deep UV radiation.
 10. The methodof claim 7 wherein the second material consists essentially of silicon.11. The method of claim 7 wherein the second material consistsessentially of conductively-doped silicon.
 12. The method of claim 7wherein the second material comprises oxygen.
 13. The method of claim 7wherein the second material comprises silicon dioxide.
 14. The method ofclaim 7 wherein the second material comprises silicon and issubstantially free of nitrogen, and the third material consistsessentially of silicon nitride.
 15. The method of claim 7 wherein thesecond material comprises conductively-doped silicon and issubstantially free of nitrogen, and the third material consistsessentially of silicon nitride.